CN111905835B - Preparation method and application of efficient photo-thermal catalytic material - Google Patents
Preparation method and application of efficient photo-thermal catalytic material Download PDFInfo
- Publication number
- CN111905835B CN111905835B CN202010889678.5A CN202010889678A CN111905835B CN 111905835 B CN111905835 B CN 111905835B CN 202010889678 A CN202010889678 A CN 202010889678A CN 111905835 B CN111905835 B CN 111905835B
- Authority
- CN
- China
- Prior art keywords
- copper oxide
- polydopamine
- stirring
- solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 39
- 229920001690 polydopamine Polymers 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000005751 Copper oxide Substances 0.000 claims description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 238000006701 autoxidation reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 241000530268 Lycaena heteronea Species 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims 4
- 229960003638 dopamine Drugs 0.000 claims 2
- 229960004643 cupric oxide Drugs 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a high-efficiency photo-thermal catalytic material, and a copper oxide-polydopamine-palladium (CuO-PDA-Pd) high-efficiency photo-thermal catalytic material obtained by the preparation method, and also relates to application of the high-efficiency photo-thermal catalytic material in catalyzing Suzuki reaction. Compared with the noble metal-palladium catalyst in the prior art, the copper oxide-polydopamine-palladium catalyst prepared by the method has lower production cost and is suitable for large-scale popularization. The copper oxide-polydopamine-palladium catalyst prepared by the method is used for catalyzing a Suzuki coupling reaction, and after the reaction is carried out for 90 minutes, the conversion rate reaches 90%, and the conversion efficiency is higher.
Description
Technical Field
The invention relates to a catalyst material, in particular to a high-efficiency photo-thermal catalytic material which can be used as a Suzuki reaction catalyst and applied to the field of organic synthesis.
Background
In recent years, since noble metal nanoparticles have high light absorptivity in a wide sunlight spectrum range including visible light and ultraviolet light, noble metal nanoparticles such as gold, silver, and the like have been recognized as a novel effective material for collecting sunlight. When noble metal nanoparticles are used for catalytic reactions, both plasma photocatalysis and photothermal heating contribute to catalytic activity. Noble metal alloys, such as gold-palladium, etc., have been reported as photo-thermal catalytic materials. Noble metal-palladium bimetallic, while having high catalytic efficiency, is extremely costly and complex synthetic processes have hampered its practical use. Reducing the cost of the catalyst is critical to facilitate its use. Recently, copper oxide (CuO) has been found to be one of the excellent photothermal materials. Therefore, copper oxide is a promising catalyst carrier, which is high in the stock of copper oxide and low in cost as compared with noble metals.
In view of this, there is a need to develop a novel photocatalytic material that is low in cost and high in efficiency.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a high-efficiency photo-thermal catalytic material, which comprises the following steps:
step (1), taking copper sulfate pentahydrate (CuSO) 4 ·5H 2 O) dissolving in water, heating to 50-60deg.C under stirring, maintaining the temperature, adding sodium hydroxide (NaOH) solution, heating to 65-75deg.C, and maintaining the temperature to obtain blue copper hydroxide (Cu (OH) 2 ）；
Step (2), adding D-glucose into the solution obtained in the step (1), and preserving the temperature of the mixture solution at 65-75 ℃; the color of the suspension gradually changed to red; centrifuging to obtain red precipitate cuprous oxide (Cu) 2 O) washing with water and ethanol for several times in sequence;
step (3), the cuprous oxide obtained in the step (2) is dispersed in NaOH solution, and is preserved for autoxidation, and the product copper oxide (CuO) is collected and washed with water and ethanol for a plurality of times in sequence;
step (4), mixing Tris buffer solution, copper oxide and Polydopamine (PDA) under stirring, stirring the mixture to obtain a product copper oxide-polydopamine (CuO-PDA), and washing for a plurality of times;
step (5), dispersing the product copper oxide-polydopamine (CuO-PDA) obtained in the step (4) in deionized water, and adding potassium tetrachloropalladate (K) 2 PdCl 4 ) The solution was stirred and then sodium borohydride (NaBH 4 ) Stirring the solution, reacting, centrifuging after the reaction is finished to obtain a product copper oxide-polydopamine-palladium (CuO-PDA-Pd), fully rinsing with water and ethanol, and drying in a decompression dryer to obtain the copper oxide-polydopamine-Pd.
In the preferred embodiment, in step (1), 0.63-2.5. 2.5 g of copper sulfate pentahydrate is dissolved in 50 mL deionized water, and more preferably 1.25 g of copper sulfate pentahydrate is dissolved in 50 mL deionized water. The concentration of NaOH solution is 2.5-3.5-M, and the addition amount is 20-40 mL; more preferably, the concentration is 3M and the addition is 30 mL. Preferably, the stirring speed is 300 rpm, the heating temperature is 55 ℃, and the incubation time is 2 min. As a preferable technical scheme, naOH solution is added and then heated to 70 ℃, and the heat preservation time is 5 min.
As a preferred embodiment, in the step (2), 0.2 to 0.4 g of D-glucose is added to the solution obtained in the step (1), and more preferably, the D-glucose is added in an amount of 0.3. 0.3 g. As a preferable technical scheme, the temperature for heat preservation is 70 ℃, and the time for heat preservation is 20 min. As a preferable technical scheme, the washing times are 3 times.
As a preferred technical scheme, in the step (3), the concentration of the NaOH solution is 0.05-0.15 and M, and the preferred concentration is 0.1M. As a preferred embodiment, the autoxidation time is 20-28 h, more preferably 24-h. As a preferable technical scheme, the washing is performed for 4-5 times.
As a preferable technical scheme, in the step (4), the pH of the Tris buffer solution is 8.2-8.8, and each 100 mL of Tris buffer solution is dissolved with 0.2-0.3-g of copper sulfate pentahydrate and 350-450 mu L of hydrogen peroxide; more preferably, the pH is 8.5, and each 100 mL Tris buffer is dissolved with 0.25. 0.25 g copper sulfate pentahydrate and 398. Mu.L hydrogen peroxide (H 2 O 2 ）。
As a preferred technical scheme, in the step (4), 40-60 mg copper oxide and 40-60 mg polydopamine are mixed in every 100 mL Tris buffer. Preferably 50mg copper oxide and 50mg polydopamine are mixed.
As a preferable technical scheme, in the step (4), the stirring speed is 400-600 rpm, and more preferable stirring speed is 500 rpm; the stirring time is 5-15 min, more preferably 10 min.
As a preferable technical scheme, in the step (5), 15-25 mg copper oxide-polydopamine is dispersed in 30-50 mL deionized water; more preferably, 20 mg copper oxide-polydopamine is dispersed in 40 mL deionized water. The concentration of the potassium tetrachloropalladate solution is 4-6 mM, and the addition amount is 3.5-4 mL; more preferably, the concentration of the potassium tetrachloropalladate solution is 5mM and the addition amount is 3.77 mL; followed by stirring for 5 min.
As a preferable technical scheme, in the step (5), the concentration of the sodium borohydride solution is 2-3 mM, and the adding amount is 35-45 mL; preferably at a concentration of 2.5 mM, 40 mL is added dropwise; the addition time was 30 min, followed by stirring reaction 3 h. As a preferred embodiment, the drying time is 24 h.
The high-efficiency photo-thermal catalytic material prepared by the invention consists of copper oxide, polydopamine and nano palladium (CuO-PDA-Pd). Copper oxide, which is a p-type semiconductor with a narrow band gap (overall volume of 1.2 eV), is a very promising material for manufacturing solar cells due to its high absorbance, low thermal emissivity, relatively good electrical properties and higher carrier concentration. Various organic-inorganic nanocomposite materials having high thermal conductivity, high electrical conductivity, high mechanical strength, and high temperature durability can also be prepared using nanoscale copper oxide.
Polydopamine can adhere to almost all material surfaces including noble metals, metal oxides, semiconductors, ceramics and synthetic polymers. Polydopamine has been used in various catalytic systems and as catalyst support due to its universal binding capacity. Polydopamine is reactive towards noble metal ions, making metal catalyst nanoparticles (e.g. gold, silver and palladium) easy to deposit in situ. Meanwhile, polydopamine membranes can also grow on virtually all substrates. In combination with these two unique functions, the catalytic metal nanoparticles can be attached to any particle or substrate with the aid of a polydopamine interlayer. And the polydopamine as a catalyst carrier does not affect the catalytic performance of the supported catalyst.
The metal palladium is a common catalyst, is commonly used for various organic synthesis reactions, in particular to nano palladium, and has higher catalytic efficiency due to higher specific surface area.
For the above reasons, the invention provides a preparation method of a copper oxide-polydopamine-palladium catalyst material and a copper oxide-polydopamine-palladium composite catalyst prepared by the method. The catalyst has excellent catalytic effect on Suzuki reaction at room temperature.
Another object of the present invention is to provide a copper oxide-polydopamine-palladium (CuO-PDA-Pd) high efficiency photocatalytic material prepared by the above method.
Another object of the present invention is to provide a use of the above copper oxide-polydopamine-palladium (CuO-PDA-Pd) high efficiency photo-thermal catalytic material as a catalyst for Suzuki reaction.
The beneficial technical effects of the invention are as follows:
(1) According to the invention, copper oxide is used as a carrier of the catalyst, and the palladium catalyst is supported by preparing copper oxide-polydopamine, so that the prepared copper oxide-polydopamine-palladium catalyst has lower production cost compared with the noble metal-palladium catalyst in the prior art, and is suitable for large-scale popularization.
(2) The copper oxide-polydopamine-palladium catalyst prepared by the method is used for catalyzing a Suzuki coupling reaction, and after the reaction is carried out for 90 minutes, the conversion rate reaches 90%, and the conversion efficiency is high.
Drawings
FIG. 1 is an SEM image of the CuO-PDA-Pd prepared in example 1 of the present invention.
FIG. 2 is an EDX analysis of CuO-PDA-Pd prepared in example 1 of the present invention.
FIG. 3 is an elemental analysis picture of CuO-PDA-Pd prepared in example 1 of the present invention.
Fig. 4 shows a Suzuki reaction system using a xenon lamp as a light source.
Detailed Description
The invention is further described below in connection with specific embodiments and the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
The preparation method of the high-efficiency photo-thermal catalytic material comprises the following steps:
dissolving 1.25 g copper sulfate pentahydrate in 50 mL water, stirring at a stirring speed of 300 rpm, heating to 55 ℃, keeping the temperature for 2 min, adding 30 mL of NaOH solution, rapidly setting the temperature to 70 ℃, and keeping the temperature for 5 min to generate blue copper hydroxide; the concentration of the NaOH solution was 3M.
Step (2), adding 0.3 g of D-glucose into the solution obtained in the step (1), and keeping the temperature of the mixture solution at 70 ℃ for about 20min; the color of the suspension gradually changed to red; and (3) centrifuging to obtain cuprous oxide as a red precipitate, and washing the red precipitate with water and ethanol for 3 times in sequence.
Step (3), the cuprous oxide obtained in the step (2) is dispersed in NaOH solution, 24 h is stored for autoxidation, and the product cupric oxide is collected and washed with water and ethanol for 3 times in sequence; the concentration of the NaOH solution was 0.1M.
Step (4), mixing 100 mL of Tris buffer solution, 50mg copper oxide and 50mg of polydopamine at a stirring speed of 500 rpm, and stirring the mixture for 10 min to obtain a copper oxide-polydopamine product, and washing 3 times; the pH of the Tris buffer solution is 8.5, and each 100 mL of Tris buffer solution is dissolved with 0.25 g pentahydrate copper sulfate and 398 mu L hydrogen peroxide.
And (5) dispersing the product copper oxide-polydopamine 20 mg obtained in the step (4) in 40 mL deionized water, adding 3.77 mL of 5mM potassium tetrachloropalladate solution, stirring for about 5 min, then dropwise adding 40 mL of 2.5 mM sodium borohydride solution, stirring for reaction, reacting for 3 h, centrifuging after the reaction is finished to obtain the product copper oxide-polydopamine-palladium (CuO-PDA-Pd), fully rinsing with water and ethanol, and drying in a reduced pressure dryer for 24 h.
The CuO-PDA-Pd composite catalytic material synthesized in example 1 was characterized. The results of the characterization are shown in fig. 1 to 3. Among them, fig. 1 is an SEM image, fig. 2 is EDX analysis, and fig. 3 is an elemental analysis picture.
It can be seen from fig. 1 to 3 that palladium has been successfully supported on a copper oxide-polydopamine support. In fig. 2, the black dots fully distributed on the surface of the copper oxide-polydopamine carrier are palladium.
Test case
The CuO-PDA-Pd prepared in example 1 was selected as a catalyst, and the catalytic activity of the catalyst on the Suzuki coupling reaction under irradiation of a xenon lamp was evaluated.
The system of the reaction is shown in FIG. 4, and the Suzuki coupling reaction is carried out under irradiation of a xenon lamp. The Suzuki coupling reaction was performed using bromobenzene and phenylboronic acid. The reaction formula is shown as the following formula (1):
(1)
The reaction steps are as follows: bromobenzene (8.4. Mu.L, 0.08 mmol), phenylboronic acid (10.9 mg,0.08 mmol), deionized water (1.5 mL), naOH (10 mg,0.25 mmol), cetyltrimethyl-ammonium bromide (CTAB, 36 mg) and CuO-PDA-Pd catalyst (2 mg) were placed in a quartz cuvette with an optical path of 1 cm and irradiated using a continuous xenon lamp (model: xenon Oriel Arc Lamp, mod. 67005, newport, UK; maximum optical power: 300W), and the reaction was stirred at 1000 rpm for 20min, 30 min, 60 min, 90 min and at room temperature (25 ℃).
The effect of the catalytic reaction is shown in table 1 below:
table 1: conversion of bromobenzene in the presence of a CuO-PDA-Pd catalyst at different reaction times under xenon irradiation
| Reaction time (min) | 20 | 30 | 60 | 90 |
| Conversion (%) | 32.8 | 57.8 | 79.9 | 90.0 |
The results in Table 1 show that the conversion of the Suzuki coupling reaction reached 90% after 90 min of reaction.
The invention provides a preparation method of a novel photo-thermal catalytic material, and the photo-thermal catalytic material prepared by the preparation method, which has high catalytic efficiency and lower cost compared with noble metal catalytic materials, and is suitable for large-scale popularization.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (4)
1. The preparation method of the high-efficiency photo-thermal catalytic material is characterized by comprising the following steps of:
dissolving 1.25 g copper sulfate pentahydrate in 50 mL deionized water, stirring at a stirring speed of 300 rpm, heating to 55 ℃, keeping the temperature for 2 min, adding 30 mL of NaOH solution, rapidly setting the temperature to 70 ℃, and keeping the temperature for 5 min to generate blue copper hydroxide; the concentration of the NaOH solution was 3M;
step (2), adding 0.3 g of D-glucose into the solution obtained in the step (1), wherein the temperature of heat preservation is 70 ℃, and the time of heat preservation is 20min; the color of the suspension gradually changed to red; centrifuging to obtain red precipitate cuprous oxide, and washing with water and ethanol for 3 times sequentially;
step (3), the cuprous oxide obtained in the step (2) is dispersed in NaOH solution and stored for autoxidation, copper oxide product is collected, and the copper oxide product is washed with water and ethanol for several times in sequence; the concentration of NaOH solution was 0.1M; the autoxidation time was 24 h; the washing times are 4-5 times;
step (4), mixing Tris buffer solution, copper oxide and dopamine under stirring, and stirring the mixture to obtain a copper oxide-polydopamine product, and washing for a plurality of times; the pH of the Tris buffer solution is 8.5, and each 100 mL of Tris buffer solution is dissolved with 0.25 g pentahydrate copper sulfate and 398 mu L hydrogen peroxide; 50mg copper oxide and 50mg dopamine were mixed per 100 mL Tris buffer; the stirring speed is 500 rpm, and the stirring time is 10 min;
dispersing the product copper oxide-polydopamine obtained in the step (4) in deionized water, adding a potassium tetrachloropalladate solution, stirring, then dropwise adding a sodium borohydride solution, stirring for reaction, centrifuging after the reaction is finished to obtain the product copper oxide-polydopamine-palladium, fully rinsing with water and ethanol, and drying in a reduced pressure dryer to obtain the copper oxide-polydopamine-palladium compound;
in the step (5), dispersing 20 mg copper oxide-polydopamine in 40 mL deionized water; the concentration of the potassium tetrachloropalladate solution is 5mM, and the addition amount is 3.77 mL; followed by stirring for 5 min.
2. The method for preparing the high-efficiency photo-thermal catalytic material according to claim 1, which is characterized in that: in the step (5), the concentration of the sodium borohydride solution is 2.5 and mM, and the dropwise addition amount is 40 and mL; reaction 3 h was then stirred; the drying time was 24 h.
3. The high-efficiency photocatalytic material obtained by the method for producing a high-efficiency photocatalytic material according to claim 1 or 2.
4. Use of a high efficiency photocatalytic material according to claim 3, characterized in that: the application is as a catalyst for the Suzuki reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010889678.5A CN111905835B (en) | 2020-08-28 | 2020-08-28 | Preparation method and application of efficient photo-thermal catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010889678.5A CN111905835B (en) | 2020-08-28 | 2020-08-28 | Preparation method and application of efficient photo-thermal catalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111905835A CN111905835A (en) | 2020-11-10 |
| CN111905835B true CN111905835B (en) | 2023-08-15 |
Family
ID=73267632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010889678.5A Active CN111905835B (en) | 2020-08-28 | 2020-08-28 | Preparation method and application of efficient photo-thermal catalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111905835B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121998B (en) * | 2021-04-13 | 2023-03-07 | 河南科技大学 | Copper-based composite material, preparation method and application thereof in field of photo-thermal conversion |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344709A (en) * | 2010-08-05 | 2012-02-08 | 广东科学技术职业学院 | Preparation method of aqueous electromagnetic shielding coating containing copper |
| CN102807246A (en) * | 2012-07-27 | 2012-12-05 | 西南交通大学 | Method for preparing branched nano-CuO (cupric oxide) particles |
| CN106694026A (en) * | 2016-12-25 | 2017-05-24 | 常州梦泰照明科技有限公司 | Preparation method of core-shell type cuprous oxide photocatalyst |
| CN107473257A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院化学研究所 | Controllable cuprous nano crystalline substance of a kind of pattern, size and its preparation method and application |
| CN107790129A (en) * | 2017-11-02 | 2018-03-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cuprous oxide/graphene visible-light photocatalyst and products thereof and application |
| CN108585018A (en) * | 2018-02-26 | 2018-09-28 | 西安理工大学 | A kind of size is less than the Cu of 100nm2The preparation method of O nanospheres |
-
2020
- 2020-08-28 CN CN202010889678.5A patent/CN111905835B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344709A (en) * | 2010-08-05 | 2012-02-08 | 广东科学技术职业学院 | Preparation method of aqueous electromagnetic shielding coating containing copper |
| CN102807246A (en) * | 2012-07-27 | 2012-12-05 | 西南交通大学 | Method for preparing branched nano-CuO (cupric oxide) particles |
| CN107473257A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院化学研究所 | Controllable cuprous nano crystalline substance of a kind of pattern, size and its preparation method and application |
| CN106694026A (en) * | 2016-12-25 | 2017-05-24 | 常州梦泰照明科技有限公司 | Preparation method of core-shell type cuprous oxide photocatalyst |
| CN107790129A (en) * | 2017-11-02 | 2018-03-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cuprous oxide/graphene visible-light photocatalyst and products thereof and application |
| CN108585018A (en) * | 2018-02-26 | 2018-09-28 | 西安理工大学 | A kind of size is less than the Cu of 100nm2The preparation method of O nanospheres |
Non-Patent Citations (1)
| Title |
|---|
| "Polydopamine nanofilms as visible light-harvesting interfaces for palladium nanocrystal catalyzed coupling reactions";Aming Xie et al.;《Catalysis Science & Technology》;20151015;第6卷;摘要和实验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111905835A (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110756225B (en) | Metal/MOFs nano catalyst and preparation method and application thereof | |
| CN111437846B (en) | Porous CoO/CoP nanotube and preparation method and application thereof | |
| CN108745382B (en) | Preparation method and application of NiCd double non-noble metal modified CdS visible-light-driven photocatalyst | |
| CN111203262B (en) | Method for rapidly preparing carbon nitride nanosheet loaded nano-copper, product and application thereof | |
| CN109731571B (en) | Catalyst for high-selectivity catalysis of methane to ethanol and preparation method and application thereof | |
| CN110124693A (en) | The composite metal ion doped deficiency semiconductor light-catalyst preparation method of graphene | |
| Guan et al. | One-step synthesis of novel Bi/Bi2SiO5 flower-like composites with highly-efficient CO2 photoreduction performance | |
| CN109482208B (en) | Method for preparing catalyst by foam nickel in-situ reduction of copper ions and subsequent heat treatment | |
| CN111905835B (en) | Preparation method and application of efficient photo-thermal catalytic material | |
| CN115069290A (en) | Nitrogen-defect-containing porous carbon nitride-loaded monoatomic copper catalyst, preparation method thereof and application thereof in light nitrogen fixation | |
| CN111715262A (en) | Preparation of palladium-gold loaded nitrogen-rich carbon nitride photocatalyst and C-C bonding | |
| CN110368979B (en) | Tubular g-C3N4/CuS/Cu2S nano composite material and preparation method and application thereof | |
| CN111326753B (en) | Supported nano electro-catalyst and preparation method and application thereof | |
| CN110064386B (en) | Tin nanoparticle modified composite photocatalytic material with oxygen vacancy stannic oxide nanosheets and preparation method thereof | |
| CN110788346B (en) | Semi-metal structure tungsten ditelluride/redox graphene compound and preparation method of copper-doped compound powder thereof | |
| CN108940326B (en) | Preparation method of visible light response zinc stannate/carbon/silver bromide nano composite photocatalyst | |
| CN112604708B (en) | Molecular sieve based monoatomic catalyst and preparation method thereof | |
| CN109092306B (en) | Preparation method of LSPR effect-based metal-modified self-doped defect-rich tin oxide nanocomposite | |
| CN110961121B (en) | Z-type photocatalyst, preparation method and application | |
| CN110327948B (en) | Ternary composite nano heterojunction photocatalyst, preparation method and application | |
| CN112657555A (en) | Monodisperse Fe-O cluster doped Ni-based metal organic framework composite photocatalyst and preparation method and application thereof | |
| CN111957334A (en) | Preparation method of composite ternary heterojunction photocatalyst | |
| CN114984965B (en) | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof | |
| CN114984979B (en) | High-performance NiS2Nano material @ C, preparation method and application thereof | |
| CN115475617B (en) | Preparation method and application of porous metal copper doped disordered carbon tube material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |